Plasma cvd apparatus, plasma cvd method, and agitating device

ABSTRACT

A plasma CVD apparatus efficiently coats the surfaces of fine particles with a thin film or super-fine particles by concentrating a plasma near the fine particles. The plasma CVD apparatus includes a chamber, a container disposed in the chamber for housing the fine particles, the container having a polygonal inner shape in a cross section substantially perpendicular to a longitudinal axis of the container, a ground shielding member for shielding a surface of the container other than a housing face, a rotation mechanism for causing the container to rotate or act as a pendulum on an axis of rotation substantially perpendicular to the cross section, an opposed electrode disposed in the container so as to face the housing face, a plasma power source electrically connected to the container, a gas introducing mechanism for introducing a raw gas into the container, and an evacuation mechanism for evacuating the chamber.

BACKGROUND OF THE INVENTION Technical Field

The present invention relates to a plasma CVD (Chemical VaporDeposition) apparatus and a plasma CVD method capable of coating thesurfaces of fine particles or electronic parts efficiently with a thinfilm or super-fine particles by concentrating a plasma near the fineparticles. Moreover, the present invention relates to an agitatingdevice for agitating fine particles or electronic parts having smalldiameters.

Background Art

FIG. 9 (A) is a cross-sectional view showing the outline of aconventional plasma CVD apparatus, and FIG. 9 (B) is a cross-sectionalview along the 7B-7B line shown in FIG. 9 (A).

The plasma CVD apparatus has a cylindrical chamber 3. Both ends of thechamber 3 are closed with chamber covers 20. Inside the chamber 3, acontainer 129 is disposed. A section of the container 129 is cylindricalas shown in FIG. 9 (B). Also, the container 129 is configured so as tohouse granular materials (fine particles) 1 constituting an object to becoated inside it. Moreover, the container 129 functions as an electrodeto be connected to a plasma power source 34 or the ground potential,wherein both are constituted so as to be switchable by a switch 32. Thesection shown in FIG. 9 (B) is a section approximately parallel to thedirection of the gravity.

The container 129 is provided with a rotation mechanism (not shown). Byrotating the container 129 as the arrow by the rotation mechanism, thegranular materials (fine particles) 1 in the container 129 are subjectedto a coating treatment through the agitation or the rotation. The axisof rotation when the container 129 is rotated by the rotation mechanismis an axis approximately parallel to the horizontal direction(orthogonal to the direction of the gravity). Moreover, the airtightness inside the chamber 3 is kept even at the time of the rotationof the container 129.

Further, the plasma CVD apparatus is provided with a raw gas introducingmechanism and an evacuation mechanism. The raw gas introducing mechanismhas a tubular gas shower electrode 24. And, the plasma CVD apparatus isprovided with a plasma power supplying mechanism. The plasma powersupplying mechanism has a plasma power source 25 connected to the gasshower electrode 24 via a switch 33, or the ground potential, whereinboth are constituted so as to be switchable by the switch 33 (seeJapanese Patent Publication No. 2006-16661 (paragraphs 83 to 92, FIG.7).

SUMMARY OF THE INVENTION

Incidentally, the above-described conventional plasma CVD apparatus cannot generate plasma intensively near fine particles 1 housed in thecontainer 129, but plasmas are generated in regions separated from fineparticles 1 in the container and plasmas spread wholly and disperse.Consequently, there is such a problem that the amount of appliedelectric power becomes large relative to the amount of coated fineparticles to be obtained to thereby lower the energy efficiency.

Moreover, since fine particles having small diameters have suchproperties that they agglutinate, it was not easy to sufficiently stirsuch fine particles.

The present invention has been achieved in consideration of theabove-described circumstances, and objects thereof are to provide aplasma CVD apparatus and a plasma CVD method capable of coating thesurfaces of fine particles or electronic parts efficiently with a thinfilm or super-fine particles by concentrating a plasma near the fineparticles or the electronic parts.

Another object of the present invention is to provide an agitatingdevice capable of sufficiently agitating fine particles or electronicparts having small diameters.

In order to solve the above problem, the plasma CVD apparatus accordingto the present invention is provided with a chamber,

a container disposed in the chamber for housing fine particles orelectronic parts, the container having a circular inner shape in asection approximately parallel to the direction of the gravity,

a ground shielding member for shielding the surface of the containerother than a housing face for housing the fine particles or theelectronic parts,

a rotation mechanism for causing the container to rotate or act as apendulum on the axis of rotation approximately perpendicular to thesection,

an opposed electrode disposed in the container so as to face the housingface,

a plasma power source electrically connected to the container,

a gas introducing mechanism for introducing a raw gas into thecontainer, and

an evacuation mechanism for evacuating the inside of the chamber,

wherein a plasma CVD method is used while agitating or rotating the fineparticles or the electronic parts in the container by using the rotationmechanism for causing the container to rotate or act as a pendulum,thereby coating the surfaces of the fine particles or the electronicparts with super-fine particles having smaller diameters than the fineparticles or the electronic parts, or with a thin film.

Meanwhile, the super-fine particles mean fine particles having smallerparticle diameters than the fine particles. States in which the surfacesof the fine particles are coated with super-fine particles include astate in which the surfaces of the fine particles are coated withsuper-fine particles continuously or discontinuously, a state in whichthe surfaces of the fine particles are coated with aggregates of thesuper-fine particles continuously or discontinuously, and a state inwhich the super-fine particles and the aggregates of the super-fineparticles are mixed and continuously or discontinuously coated.

According to the plasma CVD apparatus, the surface of the containerother than the housing face for housing the fine particles or theelectronic parts is shielded by the ground shielding member. Therefore,it is possible to generate a plasma between the housing face and theopposed electrode facing it and to concentrate a plasma electric powerto the housing face, and as the result, to supply a plasma electricpower intensively to the fine particles or the electronic parts placedon the housing face. Accordingly, by concentrating the plasma near thefine particles or the electronic parts, it becomes possible to coat thesurfaces of the fine particles or the electronic parts efficiently witha thin film or super-fine particles.

Further, in the plasma CVD apparatus according to the present invention,the container preferably has a first container member having a circularinner shape in a section, a first ring-shaped member and a secondring-shaped member disposed facing the first ring-shaped member,wherein:

each outer circumference of the first and second ring-shaped members isconnected to the inner surface of the first container member,

each inner circumference of the first and second ring-shaped members isplaced on the opposed electrode side from the inner surface of the firstcontainer member, and

the housing face is preferably formed by the surfaces of the first andsecond ring-shaped members facing each other and the inner surface ofthe first container member.

According to the plasma CVD apparatus, the housing face is formed by thesurfaces of the first and second ring-shaped members facing each otherand the inner surface of the first container member, and the surface ofthe container other than the housing face is shielded by the groundshielding member. Therefore, it is possible to generate the plasmabetween the housing face and the opposed electrode facing it and toconcentrate a plasma electric power to the housing face, and as theresult, to supply the plasma electric power intensively to fineparticles or electronic parts placed on the housing face.

The plasma CVD apparatus according to the present invention is providedwith a chamber,

a container disposed in the chamber for housing fine particles orelectronic parts, the container having a polygonal inner shape in asection approximately parallel to the direction of the gravity,

a ground shielding member for shielding the surface of the containerother than a housing face for housing the fine particles or theelectronic parts,

a rotation mechanism for causing the container to rotate or act as apendulum on the axis of rotation approximately perpendicular to thesection,

an opposed electrode disposed in the container so as to face the housingface,

a plasma power source electrically connected to the container,

a gas introducing mechanism for introducing a raw gas into thecontainer, and

an evacuation mechanism for evacuating the inside of the chamber,

wherein a plasma CVD method is used while agitating or rotating the fineparticles or the electronic parts in the container by using the rotationmechanism for causing the container to rotate or act as a pendulum,thereby coating the surfaces of the fine particles or the electronicparts with super-fine particles having smaller diameters than the fineparticles or the electronic parts, or with a thin film.

Moreover, in the plasma CVD apparatus according to the presentinvention, the container preferably has the first container memberhaving a circular inner shape in a section, a second container memberthat is disposed in the first container member and has a polygonal innershape in a section, a first ring-shaped member disposed in the firstcontainer member and placed on one side of the second container member,and a second ring-shaped member disposed in the first container memberand placed on the other side of the second container member, wherein:

each outer circumference of the first and second ring-shaped members isconnected to the inner surface of the first container member,

each inner circumference of the first and second ring-shaped members isplaced on the opposed electrode side from the inner surface of thesecond container member, and

the housing face is preferably formed by the surfaces of the first andsecond ring-shaped members facing each other and the inner surface ofthe second container member.

Further, in the plasma CVD apparatus, there may additionally be provideda ground shielding member for shielding the surface of the opposedelectrode other than an opposed surface facing the fine particles or theelectronic parts housed in the container when the rotation mechanismcauses the container to rotate or act as a pendulum.

Furthermore, in the plasma CVD apparatus, there may additionally beprovided a second plasma power source electrically connected to theopposed electrode.

Furthermore, in the plasma CVD apparatus, there may additionally beprovided a striking member for being struck against the ground shieldingmember in order to give a vibration to the fine particles or theelectronic parts housed in the container.

Moreover, in the plasma CVD apparatus, preferably there is additionallyprovided plural grounding plates disposed between one end of the firstcontainer member and the opposed electrode. Consequently, the groundingplate works as the opposed electrode to make it possible to generate aplasma between the grounding plate and the housing face. Mutualdistances between the plural grounding plates are preferably 5 mm orless, more preferably 3 mm or less.

The plasma CVD apparatus according to the present invention is providedwith a chamber,

a container disposed in the chamber for housing fine particles orelectronic parts, the container having a circular inner shape in asection approximately parallel to the direction of the gravity,

a rotation mechanism for causing the container to rotate or act as apendulum on the axis of rotation approximately perpendicular to thesection,

an opposed electrode disposed in the container so as to face the innersurface of the container,

a ground shielding member for shielding the surface of the opposedelectrode other than an opposed surface facing the fine particles or theelectronic parts housed in the container when the rotation mechanismcauses the container to rotate or act as a pendulum,

a plasma power source electrically connected to the opposed electrode,

a gas introducing mechanism for introducing a raw gas into thecontainer, and

an evacuation mechanism for evacuating the inside of the chamber,

wherein a plasma CVD method is used while agitating or rotating the fineparticles or the electronic parts in the container by using the rotationmechanism for causing the container to rotate or act as a pendulum,thereby coating the surfaces of the fine particles or the electronicparts with super-fine particles having smaller diameters than the fineparticles or the electronic parts, or with a thin film.

According to the above plasma CVD apparatus, the surface of the opposedelectrode other than the opposed surface facing the fine particles orthe electronic parts housed in the container when the rotation mechanismcauses the container to rotate or act as a pendulum is shielded by theground shielding member. Consequently, it is possible to generate aplasma between the opposed surface and the inner surface of thecontainer facing it, and to concentrate a plasma electric power to theopposed surface, and as the result, to supply the plasma electric powerintensively to the fine particles or the electronic parts housed in thecontainer. Accordingly, by concentrating the plasma near the fineparticles or the electronic parts, it becomes possible to coat thesurfaces of the fine particles or the electronic parts efficiently witha thin film or super-fine particles.

Further, in the plasma CVD apparatus according to the present invention,the minimum diameter or gap is preferably 5 mm or less, more preferably3 mm or less, in the pathway through which gas is evacuated from theinside of the container to the outside of the chamber by the evacuationmechanism. This allows the suppression of the dispersion of the plasma,and also an abnormal discharge.

Furthermore, in the plasma CVD apparatus according to the presentinvention, there may additionally be provided magnetic substanceparticles housed in the container, an electromagnet for supplyingelectromagnetic power to the magnetic substance particles, and a powersource for supplying current to the electromagnet in a pulse shape tosupply the electromagnetic power to the magnetic substance particles ina pulse shape, thereby agitating the magnetic substance particles.

The plasma CVD apparatus according to the present invention is providedwith a chamber,

a container disposed in the chamber for housing fine particles, thecontainer having a polygonal inner shape in a section approximatelyparallel to the direction of the gravity,

a rotation mechanism for causing the container to rotate or act as apendulum on the axis of rotation approximately perpendicular to thesection,

an opposed electrode disposed in the container so as to face the innersurface of the container,

a ground shielding member for shielding the surface of the opposedelectrode other than an opposed surface facing the fine particles housedin the container when the rotation mechanism causes the container torotate or act as a pendulum,

a plasma power source electrically connected to the opposed electrode,

a gas introducing mechanism for introducing a raw gas into thecontainer, and

an evacuation mechanism for evacuating the inside of the chamber,

wherein a plasma CVD method is used while agitating or rotating the fineparticles in the container by using the rotation mechanism for causingthe container to rotate or act as a pendulum, thereby coating thesurfaces of the fine particles with super-fine particles having smallerdiameters than the fine particles, or with a thin film.

The plasma CVD apparatus according to the present invention is providedwith a chamber,

a container disposed in the chamber for housing electronic parts, thecontainer having a polygonal inner shape in a section approximatelyparallel to the direction of the gravity,

a rotation mechanism for causing the container to rotate or act as apendulum on the axis of rotation approximately perpendicular to thesection,

an opposed electrode disposed in the container so as to face the innersurface of the container,

a ground shielding member for shielding the surface of the opposedelectrode other than an opposed surface facing the electronic partshoused in the container when the rotation mechanism causes the containerto rotate or act as a pendulum,

a plasma power source electrically connected to the opposed electrode,

a gas introducing mechanism for introducing a raw gas into thecontainer, and

an evacuation mechanism for evacuating the inside of the chamber,wherein a plasma CVD method is used while agitating or rotating theelectronic parts in the container by using the rotation mechanism forcausing the container to rotate or act as a pendulum, thereby coatingthe surfaces of the electronic parts with super-fine particles havingsmaller diameters than the electronic parts, or with a thin film.

Furthermore, in the plasma CVD apparatus according to the presentinvention, there may additionally be provided magnetic substanceparticles housed in the container, an electromagnet for supplyingelectromagnetic power to the magnetic substance particles, and a powersource for supplying current to the electromagnet while inverting thepolarity to supply the electromagnetic power to the magnetic substanceparticles while inverting the polarity, thereby agitating the magneticsubstance particles.

Moreover, in the plasma CVD apparatus according to the presentinvention, there may additionally be provided magnetic substanceparticles housed in the container, an electromagnet for supplyingelectromagnetic power to the magnetic substance particles, and anoscillating mechanism for oscillating the electromagnet to supply theelectromagnetic power to the magnetic substance particles whileoscillating the electromagnet, thereby agitating the magnetic substanceparticles.

Furthermore, in the plasma CVD apparatus according to the presentinvention, there may additionally be provided a power source for givingan ultrasonic vibration to the electromagnet.

Moreover, in the plasma CVD apparatus according to the presentinvention, the surfaces of the magnetic substance particles arepreferably coated with DLC fine particles or a DLC film.

In addition, in the plasma CVD apparatus according to the presentinvention, the opposed electrode preferably has a surface on the sideopposed to the direction of the gravity, which is convex to the opposedside.

Furthermore, in the plasma CVD apparatus according to the presentinvention, the plasma power source is preferably a high-frequency powersource of 50 to 500 kHz.

The plasma CVD method according to the present invention includes thesteps of housing fine particles or electronic parts in a containerhaving a circular inner shape in a section approximately parallel to thedirection of the gravity,

shielding the surface of the container other than a housing face forhousing the fine particles or the electronic parts with a groundshielding member,

disposing an opposed electrode facing the housing face in the container,

evacuating the inside of the container,

causing the container to rotate or act as a pendulum on the axis ofrotation approximately perpendicular to the section,

introducing a raw gas into the container, and

supplying a plasma power to the container to coat the surfaces of thefine particles or the electronic parts with super-fine particles havingsmaller diameters than the fine particles or the electronic parts, orwith a thin film by a plasma CVD method while agitating or rotating fineparticles or electronic parts in the container.

The plasma CVD method according to the present invention includes thesteps of housing fine particles or electronic parts in a containerhaving a polygonal inner shape in a section approximately parallel tothe direction of the gravity,

shielding the surface of the container other than a housing face forhousing the fine particles or the electronic parts with a groundshielding member,

disposing an opposed electrode facing the housing face in the container,

evacuating the inside of the container,

causing the container to rotate or act as a pendulum on the axis ofrotation approximately perpendicular to the section,

introducing a raw gas into the container, and

supplying a plasma power to the container to coat the surfaces of thefine particles or the electronic parts with super-fine particles havingsmaller diameters than the fine particles or the electronic parts, orwith a thin film by a plasma CVD method while agitating or rotating fineparticles or electronic parts in the container.

The agitating device according to the present invention is provided witha container for housing fine particles or electronic parts,

magnetic substance particles housed in the container,

an electromagnet that is disposed outside the container, and whichsupplies an electromagnetic power to the magnetic substance particles,and

a power source for supplying a current to the electromagnet in a pulseshape,

wherein an electromagnetic power is supplied to the magnetic substanceparticles in a pulse shape to stir the magnetic substance particles.

The agitating device according to the present invention is provided witha container for housing fine particles or electronic parts,

magnetic substance particles housed in the container,

an electromagnet that is disposed outside the container, and whichsupplies an electromagnetic power to the magnetic substance particles,and

a power source for supplying a current to the electromagnet whileinverting the polarity,

wherein an electromagnetic power is supplied, while inverting thepolarity, to the magnetic substance particles to stir the magneticsubstance particles.

The agitating device according to the present invention is provided witha container for housing fine particles or electronic parts,

magnetic substance particles housed in the container,

an electromagnet that is disposed outside the container, and whichsupplies an electromagnetic power to the magnetic substance particles,and

an oscillating mechanism for oscillating the electromagnet,

wherein an electromagnetic power is supplied, while oscillating theelectromagnet, to the magnetic substance particles to stir the magneticsubstance particles.

As described above, according to the present invention, it is possibleto provide a plasma CVD apparatus and a plasma CVD method capable ofcoating the surfaces of fine particles or electronic parts efficientlywith a thin film or super-fine particles by concentrating a plasma nearfine particles.

Moreover, according to another invention, it is possible to provide anagitating device capable of sufficiently agitating fine particles orelectronic parts having small diameters.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view showing a plasma CVD apparatus by anembodiment according to the present invention.

FIG. 2 is a cross-sectional view along the 2-2 line shown in FIG. 1.

FIG. 3 is a cross-sectional view showing a first modified example of theelectromagnetic agitating mechanism by an embodiment of the presentinvention.

FIG. 4 is a cross-sectional view showing a second modified example of anelectromagnetic agitating mechanism by an embodiment of the presentinvention.

FIG. 5 is a cross-sectional view showing a third modified example of anelectromagnetic agitating mechanism by an embodiment of the presentinvention.

FIG. 6 is a chart showing the analysis result of a typical DLC film byRaman spectroscopy.

FIG. 7 is a chart showing the analysis result of DLC, with which thesurfaces of PMMA fine particles are coated, by Raman spectroscopy.

FIG. 8 is a photograph taken with an optical microscope of PMMA fineparticles, the surfaces of which are coated with DLC and which have beenproduced in film-forming conditions in FIG. 7.

FIG. 9 (A) is a cross-sectional view showing the outline of aconventional plasma CVD apparatus, and FIG. 9 (B) is a cross-sectionalview along the 7B-7B line shown in FIG. 9 (A).

DESCRIPTION OF REFERENCE NUMERALS AND SIGNS

-   1. a granular material (fine particle),-   1 a. a magnetic substance particle,-   3, 13. a chamber,-   11. the direction of the gravity,-   12. an electromagnet,-   12 a. a pulse-controllable power source,-   12 b. an ultrasonic vibration-controllable electrode,-   12 c. a polarity inversion-controllable power source,-   12 d. an oscillating mechanism,-   14. a grounding rod,-   15. a ground shielding member,-   16. to 18 a grounding plate,-   19. an exhaust port,-   20, 21 a, 21 b. a chamber cover,-   20 a. a raw gas-generating source,-   21,24. a gas shower electrode,-   22. a mass flow controller (MFC),-   23, 25, 34. a plasma power source,-   26. a vacuum valve,-   27, 27 a. a ground shielding member,-   28. a ground shielding body,-   29. a first container member,-   29 a. a second container member,-   29 b. a first ring-shaped member,-   29 c. a second ring-shaped member,-   29 d. an extending portion,-   30. a container,-   31. a metal member,-   32, 33. a switch,-   129. a container,-   129 a. an inner surface constituting a polygon in the second    container member,-   129 b. the surface of the first ring-shaped member,-   129 c. the surface of the second ring-shaped member

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, embodiments of the present invention will be explained withreference to the drawings.

FIG. 1 is a cross-sectional view showing the plasma CVD apparatus by anembodiment according to the present invention. FIG. 2 is across-sectional view along the 2-2 line shown in FIG. 1. The plasma CVDapparatus is an apparatus for coating the surfaces of fine particles (orgranular materials) with super-fine particles having diameters smallerthan the fine particles, or with a thin film.

Meanwhile, in the embodiment, the plasma CVD apparatus for coating fineparticles with super-fine particles or a thin film is explained, but theplasma CVD apparatus according to the embodiment can be used as anapparatus for coating the surfaces of electronic parts having diametersof 1 mm or less, in place of the fine particles, with fine particleshaving diameters smaller than the electronic parts, or with a thin film.

Furthermore, in the embodiment, the plasma CVD apparatus, in which thecontainer having a polygonal inner shape in a section houses fineparticles and the fine particles are coated with super-fine particles,or with a thin film, is explained, but the inner shape in a section ofthe container is not limited to a polygon and is also capable of beingcircular or elliptical. The difference between the container having apolygonal inner shape in a section and the container having a circularor elliptical inner shape in a section lies in that a polygonalcontainer can coat fine particles having smaller diameters withsuper-fine particles, or with a thin film as compared with a circular orelliptical container.

As shown in FIGS. 1 and 2, the plasma CVD apparatus has the chamber 13of a cylindrical shape. One end of the chamber 13 is closed with achamber cover 21 a, and the other end of the chamber 13 is closed with achamber cover 21 b. Each of the chamber 13, and the chamber covers 21 aand 21 b is connected to the earth (ground potential).

Inside the chamber 13, the ground shielding body 28 of a cylindricalshape is disposed. One end of the ground shielding body 28 is closed,and the other end of the ground shielding body 28 is opened. The groundshielding body 28 is connected to the ground potential.

Inside the ground shielding body 28, an electroconductive container forhousing fine particles 1 is disposed. The container has a firstcontainer member 29, a second container member 29 a, a first ring-shapedmember 29 b, and a second ring-shaped member 29 c. Each of the firstcontainer member 29, the second container member 29 a, the first andsecond ring-shaped members 29 b and 29 c has conductive properties.

Inside the ground shielding body 28, the first container member 29 of acylindrical shape is disposed. One end of the first container member 29is closed, and on one end side of the first container member 29, anextending portion 29 d extending to the outside of the ground shieldingbody 28 and the chamber 13 is formed. The other end of the firstcontainer member 29 is opened. The extending portion 29 d iselectrically connected to the plasma power source 23. The plasma powersource 23 may be any of a high-frequency power source for supplyinghigh-frequency power (RF output), a power source for microwave and apower source for DC discharge, or any of a pulse-modified high-frequencypower source, power source for microwave and power source for DCdischarge.

Inside the first container member 29, the second container member 29 ais disposed, wherein the second container member 29 a has a barrel shapewith a hexagonal section as shown in FIG. 2 and the section shown inFIG. 2 is a section approximately parallel to the direction of thegravity 11. Meanwhile, in the embodiment, the second container member 29a of a hexagonal barrel shape is used, but the member is not limited toit, and a second container member of a polygonal barrel shape other thanthe hexagonal one is also capable of being employed.

One end of the second container member 29 a is attached to the inside ofthe first container member 29 by the first ring-shaped member 29 b, andthe other end of the second container member 29 a is attached to theinside of the first container member 29 by the second ring-shaped member29 c. In other words, the first ring-shaped member 29 b is placed on oneside of the second container member 29 a, and the second ring-shapedmember 29 c is placed on the other side of the second container member29 a. Each outer circumference of the first and second ring-shapedmembers is connected to the inner surface of the first container member29, and each inner circumference of the first and second ring-shapedmembers is placed on the gas shower electrode (opposed electrode) 21side, instead of the inner surface side of the second container member29 a. Moreover, the region surrounded by the first container member 29,the second container member 29 a, and the first and second ring-shapedmembers 29 b and 29 c is filled in with the metal member 31.

The distance between the first ring-shaped member 29 b and the secondring-shaped member 29 c (that is, the distance from one end to the otherend of the second container member 29 a) is smaller as compare with thedistance from one end to the other end of the first container member 29.Moreover, each of the first and second ring-shaped members 29 b and 29 cis disposed inside the first container member 29. And, it is constitutedsuch that, in a space surrounded by the inner surface of the secondcontainer member 29 a, and the first and second ring-shaped members 29 band 29 c, granular materials (fine particles) 1 as the object to becoated are housed. In other words, the inner surface 129 a constitutinga polygon in the second container member 29 a, and each of surfaces 129b and 129 c of the first and second ring-shaped members surrounding theinner surface 129 a (surfaces in which the first and second ring-shapedmembers face each other) constitute the housing face, and fine particles1 are placed over the housing face.

Moreover, it is constituted such that high-frequency power is suppliedto the second container member 29 a by the plasma power source 23 viathe first container member 29, the metal member 31 and the first andsecond ring-shaped members 29 b and 29 c. Consequently, the secondcontainer member 29 a can also function as an electrode and supply thehigh-frequency power to granular materials 1 housed inside thecontainer.

The surface of the container other than the housing face made up of theinner surface constituting a polygon 129 a of the second containermember 29 a and each of surfaces 129 b and 129 c of the first and secondring-shaped members surrounding the inner surface 129 a is covered withthe ground shielding member 27. The first container member 29, and eachof the first and second ring-shaped members 29 b and 29 c have adistance of 5 mm or less (preferably 3 mm or less) from the groundshielding member 27. The ground shielding member 27 is connected to theground potential. By covering the first container member 29, to whichhigh-frequency power is supplied, with the ground shielding member 27 asdescribed above, the high-frequency output can be concentrated insidethe second container member 29 a, and as the result, it becomes possibleto supply the high-frequency power intensively to the granular materials1 housed in the container. In other words, the present embodiment canreduce the area of a plasma source for generating plasma such as thehousing face to about ⅓ as compared with conventional plasma CVDapparatuses, and therefore, can reduce the high-frequency power amountto about ⅓ as compared with conventional plasma CVD apparatuses.

Moreover, the plasma CVD apparatus is provided with a raw gasintroducing mechanism for introducing a raw gas into the chamber 13. Theraw gas introducing mechanism has a tubular gas shower electrode(opposed electrode) 21. The gas shower electrode 21 is disposed in thesecond container member 29 a. That is, the second container member 29 ahas an opening formed on the other side thereof, and from the opening,the gas shower electrode 21 is inserted. The gas shower electrode 21 isconnected to the ground.

The surface of the gas shower electrode (opposed electrode) 21 otherthan the opposed surface facing the fine particles 1 housed in thecontainer is shielded by the ground shielding member 27 a. The groundshielding member 27 a has a distance of 5 mm or less (preferably 3 mm orless) from the gas shower electrode 21.

In the opposed surface on one side of the gas shower electrode 21, gasnozzles for ejecting a raw gas or raw gases in a shower shape areformed. The gas nozzles are disposed at the bottom portion of the gasshower electrode 21 (the opposed surface), and are disposed so as toface the granular materials 1 housed in the second container member 29a. That is, the gas nozzles are disposed so as to face the inner surfaceof the second container member 29 a. Moreover, as shown in FIG. 2, thesurface of the gas shower electrode 21 on the opposite side relative tothe direction of the gravity 11 has a convex shape toward the oppositeside. In other words, the gas shower electrode 21 has a circular orelliptical shape in a section except for the bottom portion.Consequently, even if the granular materials 1 are on the circular orelliptical portion (portion of a convex shape) when the second containermember 29 a is being rotated, the granular materials 1 can be fallenfrom the gas shower electrode 21.

The other side of the gas shower electrode 21 is connected to one sideof a mass flow controller (MFC) 22 via a vacuum valve 26. The other sideof the mass flow controller 22 is connected to a raw gas-generatingsource 20 a via a vacuum valve, a filter and the like, which are notshown. The raw gas-generating source 20 a generates different kinds ofraw gases depending on the thin film for coating the granular materials1, and for example, when a SiO₂ film is to be formed, SiH₄ gas or thelike is to be generated.

The other side of the gas shower electrode 21 is connected to one sideof a mass flow controller (MFC) that is not shown via a vacuum valve(not shown). The other side of the mass flow controller is connected toan argon gas cylinder (not shown).

The first container member 29 is provided with a rotation mechanism (notshown). The rotation mechanism causes the first container member 29 andthe second container member 29 a to rotate or act as a pendulum as thearrow shown in FIG. 2 around the gas shower electrode 21 as a rotationcenter to stir or rotate the granular materials (fine particles) 1 inthe second container member 29 a, and thus, the coating treatment iscarried out. The axis of rotation when causing the first containermember 29 and the second container member 29 a to rotate by the rotationmechanism is an axis parallel to a direction approximately parallel tothe horizontal direction (direction perpendicular to the direction ofthe gravity 11). The air tightness in the chamber 13 is retained evenduring the rotation of the first container member 29.

The plasma CVD apparatus is also provided with an evacuation system forevacuating the inside of the chamber 13. For example, the chamber 13 isprovided with plural exhaust ports 19, and the exhaust ports 19 areconnected to a vacuum pump (not shown).

Between the other end of the ground shielding body 28 and the chamber13, the ground shielding member 15 is provided. The ground shieldingmember 15 is attached to the inner surface of the chamber 13, with acrevice of 5 mm or less (preferably 3 mm or less) from the other end ofthe ground shielding body 28. In other words, the minimum diameter orgap of the pathway from the inside of the first container member 29 tothe outside of the chamber 13 through which the gas is exhausted by theevacuation system is set to be 5 mm or less (preferably 3 mm or less).It is constituted such that the raw gas introduced into the secondcontainer member 29 a from the gas shower electrode 21 passes throughthe crevice and is exhausted from the exhaust port 19. At this time, bysetting the crevice, the minimum diameter or gap to be 5 mm or less, itis possible not to keep the plasma from being confined near the granularmaterials 1 housed in the second container member 29 a. That is, whenthe crevice, the minimum diameter or gap is set to be more than 5 mm,the plasma might disperse or abnormal discharge might occur. In otherwords, by setting the crevice, the minimum diameter or gap to be 5 mm orless, the formation of a CVD film on the exhaust port 19 side can besuppressed.

Moreover, the gas shower electrode 21 has a heater (not shown). Betweenthe gas shower electrode 21 and one end of the first container member29, three grounding plates 16 to 18 are disposed. This makes it possibleto cause the discharge to occur between the inner surface of the secondcontainer member 29 a and the grounding plates 16 to 18. That is, when aCVD film of an insulator is formed on the surface of the gas showerelectrode 21 by operating the apparatus for a long time, and as theresult, when the discharge does not occur between the gas showerelectrode 21 and the second container member 29 a, the grounding plates16 to 18 work as opposed electrodes in place of the gas shower electrode21, which makes it possible to cause the discharge to occur between thegrounding plates 16 to 18 and the inner surface of the second containermember 29 a. Accordingly, by providing the grounding plates 16 to 18, itbecomes possible to operate the apparatus continuously for a long time.

The mutual distance between the grounding plates 16 to 18 is preferably5 mm or less (more preferably 3 mm or less). This can prevent a CVD filmfrom being formed in mutual gaps of grounding plates 16 to 18. As theresult, it becomes possible to operate the apparatus continuously for along time.

Moreover, the plasma CVD apparatus has a grounding rod 14 as a strikingmember for giving a vibration to the granular materials 1 housed insidethe second container member 29 a. That is, it is constituted such thatthe grounding rod 14 can be struck to the ground shielding member 27 atthe tip thereof by a driving mechanism (not shown) through openingsprovided to each of the chamber 13 and the ground shielding body 28. Bycontinuously striking the grounding rod 14 to the ground shieldingmember 27 that is rotating with the first container member 29, itbecomes possible to give a vibration to the granular materials 1 housedin the second container member 29 a. This can prevent the aggregation ofgranular materials 1 and to accelerate the agitating and mixing of thegranular materials 1. Meanwhile, the ground shielding member 27 isconnected with the first container member 29 with an insulating member,which is not shown, and therefore, it is constituted such that thevibration from the ground shielding member 27 is transmitted to thefirst container member 29 via the insulating member.

Moreover, as the plasma power source 23, the use of a high-frequencypower source of 50 to 500 kHz is preferable, and the use of ahigh-frequency power source of 100 to 300 kHz is more preferable. Theuse of a power source of such low frequency can suppress the dispersionof a plasma toward the outside of the space between the gas showerelectrode 21 and the second container member 29 a, or the space betweenthe grounding plates 16 to 18 and the second container member 29 a, ascompared with the case where a power source of a frequency of more than500 kHz is used. In other words, it is possible to confine the plasmabetween the gas shower electrode 21 and the second container member 29a, or between the grounding plates 16 to 18 and the second containermember 29 a. The use of an RF plasma of 50 to 500 kHz hardly generatesinduction heating in such a closed plasma room, that is, in the barrel(second container member 29 a), and gives sufficient V_(DC) to asubstrate when a film is formed, and therefore, a hard DLC film tends tobe easily formed as shown in the condition of film formation and resultsof film formation of Example described later. In contrast, the use ofsuch an RF plasma as 13.56 MHz hardly gives V_(DC) to a substrate in theclosed plasma room, and a hard DLC film is hardly formed as shown in thecondition of film formation and the result of film formation ofComparative Example described later as compared with Example.

Moreover, the plasma CVD apparatus also has an electromagnetic agitatingmechanism for agitating or mixing the granular materials 1 by theelectromagnet 12. The electromagnetic agitating mechanism has magneticsubstance particles 1 a housed in a container, an electromagnet 12 forsupplying electromagnetic power to the magnetic substance particle 1 a,and a pulse-controllable power source 12 a for supplying current to theelectromagnet 12 in a pulse shape. And, by supplying the electromagneticpower to the magnetic substance particle 1 a in a pulse shape, themagnetic substance particles 1 a can be stirred. In other words, therepetition of the ON/OFF of the power supply to the electromagnet 12,that is, the pulse input makes it possible to oscillate or vibrate themagnetic substance particles 1 a having been mixed with the granularmaterials 1, which makes it possible to stir or mix the granularmaterials 1. The magnetic substance particle 1 a may be one having asurface coated with DLC (Diamond Like Carbon). In this instance, thethickness of the coated DLC film is preferably about 10% of the particlediameter of the magnetic substance particle. It is considered that thecoating of DLC can reduce the friction coefficient of the surface of themagnetic substance particle to 0.2 or less, and improve the agitatingefficiency. Since DLC has a contact angle of about 80° and a highwetting property, it is considered that DLC is not adsorbed to the fineparticles 1 and can mix the fine particles 1. The magnetic substanceparticle may also be one formed by coating a thin film of a magneticsubstance over the surface of a fine particle of a nonmagneticsubstance. But, when the granular material itself being the object to becoated has a magnetic substance, the granular materials can be stirredor mixed by the electromagnetic agitating mechanism even when no othermagnetic substance particle is mixed in addition to the granularmaterial being the object to be coated. The magnetic substance particlesmay have particle sizes larger or smaller than those of the fineparticles 1 being the object to be coated.

Meanwhile, in the embodiment, the electromagnetic agitating mechanismhaving the magnetic substance particles 1 a housed in the container, theelectromagnet 12 for supplying electromagnetic power to the magneticsubstance particles 1 a, and the pulse-controllable power source 12 afor supplying current to the electromagnet 12 in a pulse shape is used,but the mechanism is not limited to it, and it may be modified andcarried out as follows.

FIG. 3 is a cross-sectional view showing a first modified example of theelectromagnetic agitating mechanism according to the embodiment of thepresent invention, wherein the same portions as those in FIG. 2 aregiven the same symbols and only different portions are explained.

As shown in FIG. 3, to the electromagnet 12, an ultrasonicvibration-controllable electrode 12 b is connected in addition to thepulse-controllable power source 12 a. This makes it possible to giveultrasonic vibrations to the electromagnet 12 and to improve theagitation performance as compared with the electromagnetic agitatingmechanism shown in FIG. 2.

The first modified example can also give the same effect as that in theabove embodiment.

FIG. 4 is a cross-sectional view showing a second modified example ofthe electromagnetic agitating mechanism according to the embodiment ofthe present invention, wherein the same portions as those in FIG. 2 aregiven the same symbols and only different portions will be explained.

As shown in FIG. 4, to the electromagnet 12, a polarityinversion-controllable power source 12 c is connected, and the powersource 12 c supplies current to the electromagnet while inversing thepolarity. This can supply electromagnetic power to the magneticsubstance particle 1 a while inversing the polarity.

The second modified example can also give the same effect as that in theabove embodiment.

Meanwhile, in the second modified example, to the electromagnet 12, anultrasonic vibration-controllable electrode can additionally beconnected.

FIG. 5 is a cross-sectional view showing a third modified example of theelectromagnetic agitating mechanism according to the embodiment of thepresent invention, wherein the same portions as those in FIG. 1 aregiven the same symbols and only different portions will be explained.

As shown in FIG. 5, to the electromagnet 12, an oscillating mechanism 12d for oscillating the electromagnet 12 is attached. This can supplyelectromagnetic power to the magnetic substance particles 1 a whileoscillating the electromagnet 12, and as the result, can stir themagnetic substance particles 1 a.

The above third modified example can also give the same effect as thatin the above embodiment.

Meanwhile, in the third modified example, to the electromagnet 12, anultrasonic vibration-controllable electrode may additionally beconnected.

Moreover, the above-described electromagnetic agitating mechanism canalso be grasped as an agitating device. That is, the agitating device isprovided with a container for housing fine particles, magnetic substanceparticles housed in the container, an electromagnet that is disposedoutside the container, and which supplies electromagnetic power to themagnetic substance particles, and a power source for supplying currentto the electromagnet. The agitating device may also adopt theabove-described first to third modified examples.

Next, a plasma CVD method for coating granular materials with super-fineparticles or a thin film by using the plasma CVD apparatus will beexplained. Here, one in which PMMA (polymethyl methacrylate) is employedas the fine particle 1 being the object to be coated and the fineparticles of PMMA are coated with DLC, will be explained as an example.

First, the granular materials (PMMA) 1 made up of plural fine particlesare housed in the second container member 29 a. The average particlediameter of the granular materials 1 is about 50 μm. Meanwhile, fineparticles of PMMA are used as the granular materials 1 here, but othergranular materials can be used. To the granular materials 1, themagnetic substance particles 1 a are mixed, wherein the surface of themagnetic substance particle is coated with a DLC film. The magneticsubstance particles 1 a are preferably used when the fine particles 1have particle diameters of 1 μm or less. That is, when particlediameters of the fine particles 1 are 1 μm or less, the stirring whilepreventing the aggregation of fine particles is difficult, and thestirring also by the magnetic substance particles 1 a is preferable. Inother words, when the fine particles 1 have particle diameters ofgreater than 1 μm, the magnetic substance particles 1 a may or may notbe used.

After that, by operating a vacuum pump, the pressure inside the chamber13 is reduced to a prescribed pressure (for example, around 5×10⁻⁵Torr). Along with this, by rotating the first container member 29 andthe second container member 29 a through the rotation mechanism, thepowders (fine particles) 1 housed inside the second container member 29a are stirred or mixed in the inside of the container. Meanwhile, here,the first container member 29 and the second container member 29 a arerotated, but the rotation mechanism can also cause the first containermember 29 and the second container member 29 a to act as a pendulum.

Subsequently, for example, toluene (C₇H₈) is generated in the rawgas-generating source 20 a as a raw gas, the flow rate of the toluene iscontrolled to 7 cc/min by the mass flow controller 22, the flow rate ofargon supplied from an argon gas cylinder is controlled to 5 cc/min, andthe toluene and argon gas with controlled flow rates are introduced intothe inside of the gas shower electrode 21. And, the toluene and argongas are ejected from the gas nozzle of the gas shower electrode 21. Thisblows the toluene and argon gas against the fine particles 1 moving inthe second container member 29 a with the agitation or rotation, and thebalance between the controlled flow rates of gases and the evacuationability maintains the pressure suitable for a film formation by the CVDmethod.

Moreover, to the ground shielding member 27 rotating with the firstcontainer member 29, the grounding rod 14 is repeatedly struck by thedriving mechanism. This can give vibration to the granular materials 1housed in the second container member 29 a, to thereby prevent theaggregation of the granular materials 1 and to accelerate the agitatingand mixing of the granular materials 1.

Further, the supply of electric power to the electromagnet 12 by a pulseinput causes the magnetic substance particles 1 a mixed with thegranular materials 1 to oscillate or vibrate, thereby accelerating theagitating and mixing of the granular materials 1.

After that, to the first container member 29, an RF output of 150 W and250 kHz is supplied from a high-frequency power source (RF power source)being an example of the plasma power source 23. This supplies an RFoutput to the second container member 29 a and the granular materials 1through the first container member 29 and the first and secondring-shaped members 29 b and 29 c. In this case, the gas showerelectrode 21 is connected to the ground potential. This ignites a plasmabetween the gas shower electrode 21 and the second container member 29a, generates a plasma in the second container member 29 a, and coats thesurfaces of fine particles 1 of PMMA with super-fine particles or a thinfilm made up of DLC. That is, since fine particles 1 are stirred androtated by rotating the second container member 29 a, the uniformcoating of a thin film over the whole surface of the fine particles 1can easily be carried out.

FIG. 6 is a chart as Comparative Example, which is the chart obtained byanalyzing a DLC film formed on a Si wafer with a plasma apparatus of aparallel plate type, by Raman spectroscopic analysis. The DLC film beingthe object to be analyzed of the chart shown in FIG. 6 was formed underthe following condition of film formation.

(Condition of Film Formation)

Plasma apparatus: parallel plate type

Output: 900 W

RF frequency: 13.56 MHzRaw gas: tolueneFlow rate of raw gas: 10 cc/minThickness of DLC film: 100 nm

FIG. 7 is a chart showing the result of the analysis of super-fineparticles or a thin film made up of DLC, with which the surfaces of fineparticles of PMMA having a particle diameter of 50 μm according to theembodiment have been coated, by Raman spectroscopy. FIG. 7 is a chartshowing the result of analyzing a typical DLC film by Ramanspectroscopy.

(Condition of Film Formation)

Plasma apparatus: polygonal barrel type apparatus in FIG. 1

Output: 150 W

RF frequency: 250 kHzRaw gas: tolueneFlow rate of toluene: 7 cc/minFlow rate of Ar: 5 cc/min

FIG. 6 shows the typical wave profile of the DLC film. By comparison ofthe wave profile shown in FIG. 6 with the wave profile shown in FIG. 7,corresponding to super-fine particles or a thin film coated on the fineparticles 1 of PMMA according to the embodiment, these wave profiles arenearly the same. Therefore, it can be said that the super-fine particlesor the thin film coated according to the embodiment is made of DLC.Accordingly, it was confirmed that the plasma CVD method according tothe embodiment can also coat the fine particles with DLC having a goodfilm quality.

FIG. 8 is a photograph of PMMA fine particles coated with DLC on thesurface produced by the condition of film formation in FIG. 7, which wastaken with an optical microscope.

PMMA fine particles are white, but there is no white fine particle inthe photograph of FIG. 8. Therefore, it can be understood that thesurface of all PMMA fine particles is coated with DLC.

Further, in the photograph of FIG. 8, each fine particle has a whitishcenter, and is deeper brown from the center towards the circumference ofthe fine particle. This shows that all particles reflect lightuniformly. If such reflection of light is uniform, DLC is transparent.Therefore, it can be said that the surfaces of all PMMA fine particlesare uniformly coated with DLC.

According to the above embodiment, by rotating the second containermember 29 a itself having a hexagonal barrel shape, it is possible torotate and stir the granular materials 1 themselves, and further, byforming the barrel into a hexagonal shape, it is possible toperiodically drop the granular materials 1 by the gravity. This candramatically improve the agitation efficiency, and can prevent theaggregation of granular materials caused by moisture or electrostaticforce, which frequently is problematic when granular materials aretreated. That is, the rotation can simultaneously and effectively carryout the agitation and the pulverization of agglutinated granularmaterials 1. Accordingly, it becomes possible to coat the fine particles1 having very small particle diameters with super-fine particles havingsmaller particle diameters than the fine particles, or with a thin film.Specifically, it becomes possible to coat fine particles having particlediameters of 50 μm or less (especially fine particles having particlediameters of 5 μm or less) with super-fine particles, or with a thinfilm.

Moreover, in the embodiment, a portion inside the first container member29 and other than portions where the second container member 29 a andthe first and second ring-shaped members 29 b and 29 c are disposed, theoutside of the first container member 29, and the side of thering-shaped member which is opposite to the space for housing thegranular materials 1 (that is, the surface of the container other thanthe housing face for housing the fine particles 1) are covered with theground shielding member 27. That is, the surface of the container otherthan the housing face for housing fine particles, which is made up ofthe inner surface 129 a constituting the polygon in the second containermember 29 a, and each of surfaces 129 b and 129 c of the first andsecond ring-shaped members surrounding the inner surface 129 a, iscovered with the ground shielding member 27. Consequently, a plasma canbe generated between the inner surface of the second container member 29a and the gas shower electrode 21 facing it. That is, it is possible toconcentrate a high-frequency output inside the second container member29 a, and as the result, to supply high-frequency power intensively tothe granular materials 1 housed inside the second container member 29 a(that is, the granular materials 1 placed on the housing face), and toeffectively supply the high-frequency power to the granular materials 1.Accordingly, it is possible to suppress the adhesion of the DLC film toportions other than the space housing the granular materials 1surrounded by the inner surface of the second container member 29 a, andthe first and second ring-shaped members 29 b and 29 c (the surface ofthe container other than the above-described housing face). It is alsopossible to make the amount of high-frequency power smaller than that ofconventional plasma CVD apparatuses.

Further, in the embodiment, by repeatedly striking the grounding rod 14against the ground shielding member 27, the agitating and mixing of thegranular materials 1 housed in the second container member 29 a can beaccelerated. The agitating and mixing of the granular materials 1 canalso be accelerated by the electromagnet 12. Accordingly, it becomespossible to coat the fine particles 1 having smaller particle diameterswith super-fine particles or a thin film made up of DLC, with a gooduniformity.

Meanwhile, the present invention is not limited to the above-describedembodiments, but can be practiced with various modifications within therange not departing from the gist of the present invention. For example,conditions of film formation for forming a thin film over the particlesmay be altered suitably.

And, in the above-described embodiment, a plasma CVD method, in whichPMMA is used as the fine particles 1 to be coated and the fine particles1 of PMMA are coated with DLC, is explained, but the use of the plasmaCVD method according to the embodiment is also possible for coating fineparticles of a material other than PMMA with super-fine particles or athin film made up of a material other than DLC.

And, when the inner shape of the container in a section is set as acircle in the above-described embodiment, for example, implementationbecomes possible by changing the plasma CVD apparatus shown in FIGS. 1and 2 to an apparatus in which the second container member 29 a and themetal member 31 are eliminated.

And, when the inner shape of the container in a section is set as anellipsoid in the above-described embodiment, for example, implementationbecomes possible by changing the plasma CVD apparatus shown in FIGS. 1and 2 to an apparatus in which the second container member 29 a and themetal member 31 are eliminated and further the inner shape of the firstcontainer member 29 in a section is set as an ellipsoid.

And, in the above-described embodiment, a constitution, in which thefirst container member 29 is connected to the plasma power source 23 andthe gas shower electrode 21 is connected to the ground potential, isemployed, but the constitution is not limited to this, and can also bechanged and practiced as follows. For example, a constitution, in whichthe first container member 29 is connected to the plasma power source 23and the gas shower electrode 21 is connected to the second plasma powersource, can also be employed. Moreover, a constitution, in which thefirst container member 29 is connected with the ground potential and thegas shower electrode 21 is connected to the plasma power source, canalso be employed, and, in this case, it may be constituted such that aplasma CVD apparatus has no ground shielding member 27. In thisinstance, the surface of the gas shower electrode (opposed electrode) 21other than the opposed surface facing the fine particles 1 housed in thecontainer is shielded by the ground shielding member 27 a. Therefore, itis possible to concentrate a high-frequency output to the opposedsurface, and, as the result, to supply high-frequency power intensivelyto the granular materials 1 housed inside the second container member 29a (that is, granular materials 1 placed on the housing face) and tosupply high-frequency power effectively to the granular materials 1.

Examples Comparative Example (Condition of Film Formation)

Plasma CVD apparatus in FIG. 1Frequency of RF power source: 13.56 MHzGlass sample: 25×75×1 mmFlow rate of C₇H₈: 7 cc/minFlow rate of Ar: 3 cc/minReaction pressure: 9.8 PaRF output: 150 WFilm time (no rotation): 30 min

(Result of Film Formation)

Film thickness: 1.325 μmKnoop hardness (5 g): 603

Example (Condition of Film Formation)

Plasma CVD apparatus in FIG. 1Frequency of RF power source: 250 kHzGlass sample: 25×75×1 mmFlow rate of C₇H₈: 7 cc/minFlow rate of Ar: 3 cc/minReaction pressure: 9.5 PaRF output: 150 WFilm time (no rotation): 30 min

(Result of Film Formation)

Film thickness: 1.153 μmKnoop hardness (5 g): 2072

In the Example, a very hard DLC film was formed. Such hard DLC film isexcellent in abrasion resistance.

1-18. (canceled)
 19. A plasma CVD method comprising the steps of: housing fine particles or electronic parts in a container having a circular inner shape in a section approximately parallel to the direction of the gravity, shielding the surface of the container other than a housing face for housing the fine particles or the electronic parts with a ground shielding member, disposing an opposed electrode facing the housing face in the container, evacuating the inside of the container, causing the container to rotate or act as a pendulum on the axis of rotation approximately perpendicular to the section, introducing a raw gas into the container, and supplying a plasma power to the container to coat the surfaces of said fine particles or said electronic parts with super-fine particles having smaller diameters than said fine particles or said electronic parts, or with a thin film by a plasma CVD method while agitating or rotating the fine particles or the electronic parts in the container.
 20. A plasma CVD method comprising the steps of: housing fine particles or electronic parts in a container having a polygonal inner shape in a section approximately parallel to the direction of the gravity, shielding the surface of the container other than a housing face for housing the fine particles or the electronic parts with a ground shielding member, disposing an opposed electrode facing the housing face in the container, evacuating the inside of the container, causing the container to rotate or act as a pendulum on the axis of rotation approximately perpendicular to the section, introducing a raw gas into the container, and supplying a plasma power to the container to coat the surfaces of said fine particles or said electronic parts with super-fine particles having smaller diameters than said fine particles or said electronic parts, or with a thin film by a plasma CVD method while agitating or rotating the fine particles or the electronic parts in the container. 21-23. (canceled) 